We propose a new residual-based a posteriori error estimator for discontinuous Galerkin discretizations of time-harmonic Maxwell's equations in first-order form. We establish that the estimator is reliable and efficient, and the dependency of the reliability and efficiency constants on the frequency is analyzed and discussed. The proposed estimates generalize similar results previously obtained for the Helmholtz equation and conforming finite element discretization of Maxwell's equations. In addition, for the discontinuous Galerkin scheme considered here, we also show that the proposed estimator is asymptotically constantfree for smooth solutions. We also present two-dimensional numerical examples that highlight our key theoretical findings and suggest that the proposed estimator is suited to drive h and hp-adaptive iterative refinements.